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ES2603056T3 - Coating composition - Google Patents

Coating composition Download PDF

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Publication number
ES2603056T3
ES2603056T3 ES10799197.8T ES10799197T ES2603056T3 ES 2603056 T3 ES2603056 T3 ES 2603056T3 ES 10799197 T ES10799197 T ES 10799197T ES 2603056 T3 ES2603056 T3 ES 2603056T3
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mol
formula
bis
prepolymer
independently
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Spanish (es)
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Peter J. Schreiber
Samuel L. Lane
Paul L. Wiggins
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Albemarle Corp
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Albemarle Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02Polyureas
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225Polyamines
    • C08G18/3237Polyamines aromatic
    • C08G18/3243Polyamines aromatic containing two or more aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/12Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/12Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

Una composición que comprende: a) una composición de curado de amina que comprende: (i) del 60 % en moles al 90 % en moles de una diamina secundaria bis-aromática que tiene la Fórmula I**Fórmula** en la que cada R1 es independientemente un alquilo C1-C10; y (ii) del 10 % en moles al 40 % en moles de una diamina primaria bis-aromática que tiene la Fórmula II**Fórmula** en la que cada R2 es independientemente un alquilo C1-C10; y cada R3 es independientemente cloro, bromo, flúor o hidrógeno, y en la que el % en moles se basa en los moles totales de la diamina secundaria bisaromática y la diamina primaria bis-aromática; y (b) un prepolímero que tiene grupos isocianato (NCO) libres; en la que la razón molar de los grupos NCO en el prepolímero con respecto a los grupos amina (-NH2) en la composición de curado de amina oscila desde 0,8 hasta 2,0.A composition comprising: a) an amine curing composition comprising: (i) from 60 mol% to 90 mol% of a bis-aromatic secondary diamine having Formula I ** Formula ** in which each R1 is independently a C1-C10 alkyl; and (ii) from 10 mol% to 40 mol% of a bis-aromatic primary diamine having Formula II ** Formula ** in which each R2 is independently a C1-C10 alkyl; and each R3 is independently chlorine, bromine, fluorine or hydrogen, and in which the mole% is based on the total moles of the bisaromatic secondary diamine and the bis-aromatic primary diamine; and (b) a prepolymer having free isocyanate (NCO) groups; wherein the molar ratio of the NCO groups in the prepolymer with respect to the amine groups (-NH2) in the amine curing composition ranges from 0.8 to 2.0.

Description

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minutos. Esto permitirá un tiempo suficiente para que los componentes se mezclen y se apliquen, puesto que estos recubrimientos se aplican normalmente mediante operaciones manuales en las que los trabajadores usan una paleta, una espátula o un peine. minutes This will allow sufficient time for the components to be mixed and applied, since these coatings are normally applied by manual operations in which workers use a trowel, a spatula or a comb.

Es también deseable que el recubrimiento tenga ciertas propiedades mecánicas de película especialmente cuando It is also desirable that the coating have certain mechanical properties of film especially when

5 se usa como recubrimiento impermeable. Por ejemplo, la norma industrial japonesa para recubrimientos de tejados (JIS A 6021) requiere que la resistencia a la tracción a 20°C sea mayor que 245,2 N/cm2 (356 psi), la resistencia al desgarro a 20°C será mayor que 147 N/cm (84 lb/pulgada), y el alargamiento de rotura a 20°C será mayor que el 450%. La dureza del recubrimiento será mayor que 30 o preferiblemente mayor que 50 en la escala de dureza Shore 5 is used as waterproof coating. For example, the Japanese industrial standard for roof coverings (JIS A 6021) requires that the tensile strength at 20 ° C be greater than 245.2 N / cm2 (356 psi), the tear strength at 20 ° C will be greater than 147 N / cm (84 lb / inch), and the elongation at break at 20 ° C will be greater than 450%. The hardness of the coating will be greater than 30 or preferably greater than 50 on the Shore hardness scale

A. El recubrimiento de la presente invención puede usarse como recubrimiento impermeable para tejados, suelos o 10 superficies expuestas a condiciones de exteriores, tales como suelos de hormigón. A. The coating of the present invention can be used as a waterproof coating for roofs, floors or surfaces exposed to outdoor conditions, such as concrete floors.

Los siguientes Ejemplos ilustran la presente invención. Ha de entenderse, sin embargo, que la invención, tal como se describe plenamente en el presente documento y tal como se enuncia en las reivindicaciones, no pretende limitarse a los detalles de los siguientes Ejemplos. The following Examples illustrate the present invention. It is to be understood, however, that the invention, as fully described herein and as set forth in the claims, is not intended to be limited to the details of the following Examples.

Ejemplos Examples

15 Ejemplo 1 Preparación de recubrimiento de poliuretano usando la composición de curado de SBMDA/MDEA 80/20 Example 1 Preparation of polyurethane coating using the curing composition of SBMDA / MDEA 80/20

Se cargaron 100 g de un prepolímero de TDI (NCO al 3,52% Airthane® PPT-80a, Air Products and Chemicals) en un vaso de precipitados de plástico de 500 ml. Se añadieron en capas 50 g de carbonato de calcio encima del prepolímero. En un vaso de precipitados separado, se disolvieron 2,17 g de 4,4’-metilen-bis-(2,6-dietilanilina) 100 g of a TDI prepolymer (3.52% Airthane® PPT-80a NCO, Air Products and Chemicals) was loaded into a 500 ml plastic beaker. 50 g of calcium carbonate were added in layers on top of the prepolymer. In a separate beaker, 2.17 g of 4,4′-methylene-bis- (2,6-diethylaniline) were dissolved

20 (MDEA) (Lonzacure® M-DEA de Lonza Group Ltd) en 8,67 g de 4,4’-bis-(sec-butilamino)difenilmetano (SBMDA) (Ethacure® 420 de Albemarle Corporation) y 39,2 g de ftalato de dioctilo (DOP) de Sigma-Aldrich Corporation. Esta composición de combinación de curado de amina consistía en una razón molar de SBMDA/MDEA de 80/20. 20 (MDEA) (Lonzacure® M-DEA from Lonza Group Ltd) in 8.67 g of 4,4'-bis- (sec-butylamino) diphenylmethane (SBMDA) (Ethacure® 420 from Albemarle Corporation) and 39.2 g of dioctyl phthalate (PDO) from Sigma-Aldrich Corporation. This amine curing combination composition consisted of a molar ratio of SBMDA / MDEA of 80/20.

Una vez disuelta, la composición de combinación de curado de amina se vertió encima del carbonato de calcio. El agente de curado, carbonato de calcio y prepolímero se agitaron usando un agitador mecánico equipado con una Once dissolved, the amine curing combination composition was poured over the calcium carbonate. The curing agent, calcium carbonate and prepolymer were stirred using a mechanical stirrer equipped with a

25 paleta agitadora de 3 hélices de 2,5 pulgadas fijada a 1000 rpm. La mezcla se agitó durante 1,5 minutos. Se vertieron 20 ml de la mezcla en un vial dracma de 30 ml y se colocó bajo un viscosímetro, entonces se usó para medir el aumento de viscosidad en la mezcla. Un viscosímetro Brookfield DV-I equipado con un husillo RV-7 se usó para determinar la vida útil del recubrimiento. La vida útil se definió como el tiempo desde el final del mezclado hasta el momento en el que la viscosidad alcanzó 100.000 cPs (documento US 5.688.892). 25 stirring blade of 3 2.5-inch propellers set at 1000 rpm. The mixture was stirred for 1.5 minutes. 20 ml of the mixture was poured into a 30 ml drachma vial and placed under a viscometer, then used to measure the increase in viscosity in the mixture. A Brookfield DV-I viscometer equipped with an RV-7 spindle was used to determine the life of the coating. The shelf life was defined as the time from the end of mixing until the time when the viscosity reached 100,000 cPs (US 5,688,892).

30 El resto de la mezcla se vertió sobre un pedazo de 8 pulgadas x 11 pulgadas de papel antiadhesivo fijado a una superficie plana, a nivel horizontal con raíles de aluminio de 1/8 pulgadas sujetados a los 3 bordes del sustrato. La mezcla se vertió en un extremo del molde y se arrastró hasta el extremo abierto del molde. La mezcla en exceso se alejó del molde. El grosor típico de los recubrimientos resultantes eran de aproximadamente 0,1 pulgadas (2,5 mm) 30 The rest of the mixture was poured onto an 8-inch x 11-inch piece of non-stick paper attached to a flat surface, horizontally with 1/8 inch aluminum rails attached to the 3 edges of the substrate. The mixture was poured into one end of the mold and dragged to the open end of the mold. The excess mixture moved away from the mold. The typical thickness of the resulting coatings was approximately 0.1 inches (2.5 mm)

La temperatura de las formulaciones y los moldes eran temperatura ambiente, 23-24 °C. La vida útil resultante fue The temperature of the formulations and molds were room temperature, 23-24 ° C. The resulting useful life was

35 de 88 minutos. El recubrimiento reposó sin alteraciones durante 7 días a temperatura ambiente para permitir el curado completo. El recubrimiento se cortó en las formas de prueba apropiadas para realizar las pruebas de propiedades físicas a aproximadamente 24°C. (Resistencia a la tracción ASTM D-412; Resistencia al desgarro ASTM D-624; dureza ASTM D-2240). 35 of 88 minutes. The coating rested unchanged for 7 days at room temperature to allow complete cure. The coating was cut in the appropriate test forms to perform physical property tests at approximately 24 ° C. (Tensile strength ASTM D-412; Tear resistance ASTM D-624; hardness ASTM D-2240).

Ejemplos 2-4 Preparación de recubrimiento de poliuretano usando la composición de curado de 40 SBMDA/MDEA Examples 2-4 Preparation of polyurethane coating using the 40 SBMDA / MDEA curing composition

Se repitió el mismo procedimiento que en el Ejemplo 1, con la excepción de que se modificó la relación molar de la composición de combinación de curado de amina MDEA y SBMDA. Se añadió suficiente DOP para llevar la masa del agente de curado hasta 50 g, o ½ de la masa del prepolímero. La masa total de la mezcla fue de 200 g en cada ejemplo. La vida útil y las propiedades mecánicas para estos ejemplos se muestran en la Tabla 1. The same procedure as in Example 1 was repeated, with the exception that the molar ratio of the MDEA and SBMDA amine curing combination composition was modified. Enough PDO was added to bring the curing agent mass to 50 g, or ½ of the prepolymer mass. The total mass of the mixture was 200 g in each example. The shelf life and mechanical properties for these examples are shown in Table 1.

45 Ejemplos 5-7 Preparación de recubrimiento de poliuretano usando la composición de curado de SBMDA/MDEA/DETDA Examples 5-7 Preparation of polyurethane coating using the curing composition of SBMDA / MDEA / DETDA

Se usó el mismo procedimiento que en el Ejemplo 1, con la excepción de que la composición de combinación de curado de amina consiste en una combinación ternaria de SBMDA, MDEA y DETDA (Ethacure® 100 de Albemarle Corporation). Se añadió suficiente DOP para llevar la masa del agente de curado hasta 50 g, o ½ la masa del The same procedure as in Example 1 was used, with the exception that the amine curing combination composition consists of a ternary combination of SBMDA, MDEA and DETDA (Ethacure® 100 from Albemarle Corporation). Enough PDO was added to bring the curing agent mass to 50 g, or ½ the mass of the

50 prepolímero. La masa total de la mezcla fue de 200 g en cada ejemplo. La vida útil y las propiedades mecánicas para estos ejemplos se muestran en la Tabla 1. 50 prepolymer The total mass of the mixture was 200 g in each example. The shelf life and mechanical properties for these examples are shown in Table 1.

7 7

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Claims (1)

imagen1image 1 imagen2image2 imagen3image3
ES10799197.8T 2009-12-17 2010-12-16 Coating composition Active ES2603056T3 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US28751209P 2009-12-17 2009-12-17
US287512P 2009-12-17
PCT/US2010/060775 WO2011084602A1 (en) 2009-12-17 2010-12-16 Coating composition

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ES2603056T3 true ES2603056T3 (en) 2017-02-23

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US (1) US8536297B2 (en)
EP (1) EP2513181B1 (en)
JP (2) JP5700857B2 (en)
KR (1) KR101777432B1 (en)
CN (1) CN102656203B (en)
AU (1) AU2010339891B2 (en)
BR (1) BR112012014557B1 (en)
CA (1) CA2783776C (en)
DK (1) DK2513181T3 (en)
ES (1) ES2603056T3 (en)
RU (1) RU2553260C2 (en)
SG (1) SG181654A1 (en)
TW (1) TWI465473B (en)
WO (1) WO2011084602A1 (en)

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GB2478343A (en) * 2010-03-05 2011-09-07 Hexcel Composites Ltd Asymmetric bis-aniline resin curing agent
US9797097B2 (en) * 2012-05-29 2017-10-24 3M Innovative Properties Company Pavement marking compositions
JP6187964B2 (en) * 2013-07-16 2017-08-30 アイシーケイ株式会社 Fast-curing, two-component, environmentally-friendly urethane waterproof material composition
CN107138104B (en) * 2017-05-22 2019-10-29 天津晶润锐拓科技发展有限公司 A kind of preparation method of the microcapsules of common cladding hindered amines stabilizer, Hinered phenols stabilizer and organic dyestuff
KR101992921B1 (en) 2018-12-28 2019-06-25 지혜경 A chain extender compositions for polyurethane
KR102298880B1 (en) 2019-10-23 2021-09-07 (주)건용 Eco-friendly polyurethane chain extender composition
US20230019038A1 (en) * 2019-12-11 2023-01-19 Ppg Industries Ohio, Inc. Compositions containing thermally conductive fillers
WO2021211184A1 (en) * 2020-04-15 2021-10-21 Ppg Industries Ohio, Inc. Compositions containing thermally conductive fillers

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US3979126A (en) * 1971-01-27 1976-09-07 Acushnet Company Ball and process and composition of matter for production thereof
GB1341018A (en) * 1971-04-19 1973-12-19 Ici Ltd Manufacture of methylene bridges polyparylamines
JP3114557B2 (en) 1994-04-21 2000-12-04 保土谷化学工業株式会社 Method for producing cold-curable fast-curing polyurethane coating waterproofing material
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JP3112250B2 (en) * 1996-07-31 2000-11-27 アイシーケイ株式会社 Polyurethane waterproof coating film forming material for on-site construction
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AU2010339891A1 (en) 2012-07-05
CA2783776C (en) 2017-01-17
KR20120114259A (en) 2012-10-16
EP2513181B1 (en) 2016-08-17
BR112012014557A2 (en) 2016-08-16
TW201202286A (en) 2012-01-16
KR101777432B1 (en) 2017-09-11
DK2513181T3 (en) 2016-09-19
CN102656203A (en) 2012-09-05
WO2011084602A1 (en) 2011-07-14
JP5925864B2 (en) 2016-05-25
US20120252971A1 (en) 2012-10-04
AU2010339891B2 (en) 2013-09-26
BR112012014557B1 (en) 2019-12-17
RU2012130100A (en) 2014-01-27
JP2015091965A (en) 2015-05-14
CN102656203B (en) 2014-09-03
RU2553260C2 (en) 2015-06-10
SG181654A1 (en) 2012-07-30
US8536297B2 (en) 2013-09-17
CA2783776A1 (en) 2011-07-14
EP2513181A1 (en) 2012-10-24
TWI465473B (en) 2014-12-21
JP2013514455A (en) 2013-04-25
JP5700857B2 (en) 2015-04-15

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